CN1927855B - Preparation method for maleic anhydride addition compound of dicyclopentadiene - Google Patents
Preparation method for maleic anhydride addition compound of dicyclopentadiene Download PDFInfo
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- CN1927855B CN1927855B CN200610122485A CN200610122485A CN1927855B CN 1927855 B CN1927855 B CN 1927855B CN 200610122485 A CN200610122485 A CN 200610122485A CN 200610122485 A CN200610122485 A CN 200610122485A CN 1927855 B CN1927855 B CN 1927855B
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Abstract
The present invention discloses preparation process of maleic anhydride addition compound of dicyclopentadinene. The preparation process includes the following steps: heating maleic anhydride to 100-130 deg.c and maintaining for 20-60 min for complete smelting; adding dicyclopentadinene while stirring, heating to 150-160 deg.c and introducing protecting nitrogen to reaction for 20-60 min; heatingto 170-180 deg.c and maintaining the temperature to further react for 3-15 hr; standing for crystallizing, suction filtering to collect the crystallisate, and stoving to obtain the maleic anhydride addition compound of dicyclopentadinene. The process has high yield and high product quality, and the product has smelting point over 80 deg.c and softening point up to 164-165 deg.c.
Description
Technical field
The present invention relates to chemical technology field, particularly a kind of preparation method of maleic anhydride addition compound of cyclopentadiene.
Background technology
Dicyclopentadiene is the by product of petroleum cracking system ethene and coal coking; contain a plurality of unsaturated double-bonds, chemical property is very active, is the most active a kind of in the norbornylene; can react with multiple compound, and can generate miscellaneous derivative, affixture.With the dicyclopentadiene is that the application of raw material synthetic low-molecular-weight organic compound is very extensive, can be used as thermo-stabilizer, fire retardant and softening agent etc. and is used for polymeric material field.The seventies, become external focus gradually as the research that modified component is applied to the synthetic resins aspect with dicyclopentadiene.In addition, be that the method that altered contents prepares modified paint and tackiness agent is also just obtaining increasingly extensive research and application with the dicyclopentadiene.
At home, reported methyne tetrahydro-phthalic anhydride in employing dicyclopentadiene and the MALEIC ANHYDRIDE generation addition reaction preparation in " insulating material " fifth phase in 1996 and " chemical engineer " second phase in 2002, interior then methyne tetrahydro-phthalic anhydride prepares Synolac with the vegetables oil polycondensation; But do not report the concrete addition reaction technology of dicyclopentadiene and MALEIC ANHYDRIDE and the characterization data of interior methyne tetrahydro-phthalic anhydride product.
Therefore, in the preparation field of the maleic anhydride addition compound of cyclopentadiene, a kind of effective preparation method need be provided, can utilize cheap raw material preparing to go out to have the maleic anhydride addition compound of high-quality cyclopentadiene by this method, and this affixture can further be prepared the high-quality Synolac with excellent mechanical performances and air-drying property with vegetables oil, dibasic alcohol and phthalic anhydride generation polycondensation.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, provide that a kind of environmental friendliness, cost are low, the preparation method of the maleic anhydride addition compound of the simple cyclopentadiene of technology.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of maleic anhydride addition compound of cyclopentadiene comprises the steps:
(1) at first MALEIC ANHYDRIDE is heated to 100 ℃～130 ℃, is incubated 20～60 minutes, make its complete fusion;
(2) warming while stirring to 150 ℃ then～160 ℃ adds dicyclopentadiene, feeds nitrogen protection, and insulation reaction 20～60 minutes;
(3) be warming up to 170 ℃～180 ℃ again, and insulation reaction 3～15 hours;
(4) leave standstill crystallization then, and suction filtration collects crystallisate, obtain the maleic anhydride addition compound of cyclopentadiene after the oven dry.
In the step 2, the mol ratio of described dicyclopentadiene and MALEIC ANHYDRIDE is 1: 1.5～4.
In the step 4, earlier the crystallisate of collecting behind the suction filtration is dissolved in the mixing solutions of normal hexane and vinyl acetic monomer, intensification makes the crystallisate dissolving, slowly cooling makes its crystallization then, refilter, drying, obtain the maleic anhydride addition compound of cyclopentadiene at last. the mixing solutions of described normal hexane and vinyl acetic monomer is that normal hexane and vinyl acetic monomer are by 1: 1～3 volume ratio blended solution.
In the step 4, earlier the crystallisate of collecting behind the suction filtration is dissolved in the mixing solutions of normal hexane and tetrahydrofuran (THF), heating up makes the crystallisate dissolving, and slowly lowering the temperature then makes its crystallization, refilters, drying, obtains the maleic anhydride addition compound of cyclopentadiene at last.The mixing solutions of described normal hexane and tetrahydrofuran (THF) is that normal hexane and tetrahydrofuran (THF) are by 1: 1～3 volume ratio blended solution.
Above-mentioned addition reaction is preferably in the reactor that has reflux condensing tube to be carried out, and preferably dry anhydrous in the reactor, in case the MALEIC ANHYDRIDE hydrolysis.
In the above-mentioned addition reaction, dicyclopentadiene is joined in the fused MALEIC ANHYDRIDE, and, can guarantee that dicyclopentadiene fully is cracked into cyclopentadiene 150 ℃～160 ℃ insulation reaction 20～60 minutes.Be warming up to 170 ℃～180 ℃ then, and insulation reaction 3～15 hours, the Diels-Alder diene synthesis takes place with MALEIC ANHYDRIDE and reacts the maleic anhydride addition compound that obtains cyclopentadiene in the cyclopentadiene that cracking is generated.In above-mentioned addition reaction, too high or too low temperature all can cause side reaction to produce.
The present invention compared with prior art has following advantage and effect:
(1) maleic anhydride addition compound of the cyclopentadiene for preparing of the present invention, productive rate is higher.
(2) quality of product is higher, and the product fusing point is more than 80 ℃, and softening temperature can reach 164～165 ℃.
(3) cost of material that adopts of this preparation method is cheap and conveniently be easy to get.
(4) the simple and environmental protection of this preparation method technology.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
Use 10 liters of stainless steel cauldrons, add 3.85 kilograms of MALEIC ANHYDRIDE, be warming up to 120 ℃ of insulations 45 minutes, after treating its complete fusion, start stirring, be warming up to 160 ℃ and add 2.9 kilograms of dicyclopentadiene, feed nitrogen protection, be incubated and after 30 minutes reaction mass be warming up to 174 ℃, insulation reaction 9 hours; After then reaction mass being cooled to about 140 ℃, be poured in the exsiccant holding tank, leave standstill etc. to be crystallizedly, bleed then to filter and collect crystallisate, promptly obtain the maleic anhydride addition compound that fusing point is the cyclopentadiene about 84 ℃ in oven dry about 100 ℃.
Embodiment 2
15 liters of 4.0 kilograms of MALEIC ANHYDRIDE addings are had in the dry anhydrous reactor of reflux condensing tube, be warming up to 130 ℃ of insulations 1.0 hours, after treating its complete fusion, start stirring, be warming up to 158 ℃ and add 2.69 kilograms of dicyclopentadiene, feed nitrogen protection, be incubated and after 40 minutes reaction mass be warming up to 180 ℃, insulation reaction 12 hours; After then reaction mass being cooled to about 130 ℃, be poured in the exsiccant holding tank, leave standstill etc. to be crystallizedly, bleed then to filter and collect crystallisate.Again with this crystallisate rising temperature for dissolving (volume ratio of normal hexane and vinyl acetic monomer is 1: 2 in the mixing solutions) in the mixing solutions of normal hexane and vinyl acetic monomer, slowly cooling makes its complete crystallization then, refilter, promptly obtaining fusing point in oven dry about 100 ℃ is about 87 ℃, and purity is the maleic anhydride addition compound of the cyclopentadiene more than 95%.
Embodiment 3
10 liters of 3.0 kilograms of MALEIC ANHYDRIDE addings are had in the dry anhydrous reactor of reflux condensing tube, be warming up to 130 ℃ of insulations 0.5 hour, after treating its complete fusion, start stirring, be warming up to 158 ℃ and add 1.34 kilograms of dicyclopentadiene, feed nitrogen protection, be incubated and after 30 minutes reaction mass be warming up to 171 ℃, insulation reaction 6 hours; After then reaction mass being cooled to about 130 ℃, be poured in the exsiccant holding tank, leave standstill etc. to be crystallizedly, bleed then to filter and collect crystallisate, promptly obtain the maleic anhydride addition compound that fusing point is the cyclopentadiene about 78 ℃ in oven dry about 100 ℃.
Claims (6)
1. the preparation method of the maleic anhydride addition compound of a cyclopentadiene is characterized in that comprising the steps:
(1) at first MALEIC ANHYDRIDE is heated to 100 ℃～130 ℃, is incubated 20～60 minutes, make its complete fusion;
(2) warming while stirring to 150 ℃ then～160 ℃ adds dicyclopentadiene, feeds nitrogen protection, and insulation reaction 20～60 minutes;
(3) be warming up to 170 ℃～180 ℃ again, and insulation reaction 3～15 hours;
(4) leave standstill crystallization then, and suction filtration collects crystallisate, obtain the maleic anhydride addition compound of cyclopentadiene after the oven dry.
2. the preparation method of the maleic anhydride addition compound of cyclopentadiene according to claim 1, it is characterized in that: in the step 2, the mol ratio of described dicyclopentadiene and MALEIC ANHYDRIDE is 1: 1.5～4.
3. the preparation method of the maleic anhydride addition compound of cyclopentadiene according to claim 1, it is characterized in that: in the step 4, earlier the crystallisate of collecting behind the suction filtration is dissolved in the mixing solutions of normal hexane and vinyl acetic monomer, intensification makes the crystallisate dissolving, slowly cooling makes its crystallization then, refilter, drying, obtain the maleic anhydride addition compound of cyclopentadiene at last.
4. the preparation method of the maleic anhydride addition compound of cyclopentadiene according to claim 3 is characterized in that: the mixing solutions of described normal hexane and vinyl acetic monomer is that normal hexane and vinyl acetic monomer are by 1: 1～3 volume ratio blended solution.
5. the preparation method of the maleic anhydride addition compound of cyclopentadiene according to claim 1, it is characterized in that: in the step 4, earlier the crystallisate of collecting behind the suction filtration is dissolved in the mixing solutions of normal hexane and tetrahydrofuran (THF), intensification makes the crystallisate dissolving, slowly cooling makes its crystallization then, refilter, drying, obtain the maleic anhydride addition compound of cyclopentadiene at last.
6. the preparation method of the maleic anhydride addition compound of cyclopentadiene according to claim 5 is characterized in that: the mixing solutions of described normal hexane and tetrahydrofuran (THF) is that normal hexane and tetrahydrofuran (THF) are by 1: 1～3 volume ratio blended solution.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200610122485A CN1927855B (en) | 2006-09-28 | 2006-09-28 | Preparation method for maleic anhydride addition compound of dicyclopentadiene |
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| CN200610122485A CN1927855B (en) | 2006-09-28 | 2006-09-28 | Preparation method for maleic anhydride addition compound of dicyclopentadiene |
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| CN1927855B true CN1927855B (en) | 2010-05-12 |
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| CN101760115A (en) * | 2009-11-30 | 2010-06-30 | 北方涂料工业研究设计院 | Preparation method of low shrink air dry vinyl ester heavy-duty anti-corrosive paint |
| CN103848801B (en) * | 2012-11-30 | 2017-07-07 | 四川科瑞德制药股份有限公司 | The preparation of outer methylene THPA and process for purification and its application in Tandospirone is prepared |
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Non-Patent Citations (6)
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| 朱培玉等.双环戊二烯改性不饱和聚酯树脂的合成研究.上海化工 3、4.1999,(3、4),28-31. |
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| 舒新华.双环戊二烯改性不饱和聚脂树脂的制备.江苏化工26 3.1998,26(3),19-23. * |
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